Method for methanol production (variants)

FIELD: technology for production of methanol from syngas.

SUBSTANCE: claimed method includes mixing of hydrocarbon raw material with water steam to provide syngas by steam conversion of hydrocarbon raw material and subsequent methanol synthesis therefrom. Conversion of hydrocarbon raw material and methanol synthesis are carried out under the same pressure from 4.0 to 12.0 MPa. In one embodiment hydrocarbon raw material is mixed with water steam and carbon dioxide to provide syngas by steam/carbonic acid conversion of hydrocarbon raw material in radial-helical reactor followed by methanol synthesis therefrom under the same pressure (from 4.0 to 12.0 MPa). In each embodiment methanol synthesis is carried out in isothermal catalytic radial-helical reactor using fine-grained catalyst with grain size of 1-5 mm. Methanol synthesis is preferably carried out in two steps with or without syngas circulation followed by feeding gas from the first or second step into gasmain or power plant.

EFFECT: simplified method due to process optimization.

12 cl, 3 tbl, 3 dwg

 

The invention relates to methods of producing methanol from a hydrocarbon and can be used in gas, chemical, petrochemical, oil refining and other industries.

Methanol is widely used in many industries as a solvent, as a starting material for polymeric materials, organic dyes, drugs and other

Methanol can be produced from hydrocarbons, e.g. natural gas, associated gas in oil, naphtha. The main raw material for methanol production is natural gas.

The main industrial method of production of methanol is the synthesis-gas steam, or steam-oxygen propakistani the conversion of natural gas with subsequent synthesis of methanol by the recovery of oxide and carbon dioxide with hydrogen on the catalyst.

Steam conversion of natural gas injection, carbon dioxide (propability conversion) provides a more optimal ratio of reactants in the source gas mixture for methanol synthesis.

The main stages of production of methanol are:

- compression of natural gas up to the pressure of the synthesis gas production;

- cleaning of natural gas feedstock from sulfur compounds;

- obtaining synthesis gas;

- com is armirovanie synthesis gas and the circulating gas to a pressure of synthesis of methanol;

the methanol synthesis;

- rectification.

Synthesis gas for the production of methanol receive in tubular furnaces of steam conversion of hydrocarbons at a pressure of 1.5-2.0 MPa and mine reactors steam-oxygen conversion of hydrocarbons at pressures up to 7.5 MPa. Sometimes these processes combine, by conducting a conversion process in two stages at pressures up to 4.0 MPa.

The methanol synthesis is performed on high-temperature zinc-chromium catalyst at a temperature of 310-400°and the pressure of 27.5-43,1 MPa or low-temperature zinc-copper-aluminum or zinc-chromium-copper catalyst at a temperature of 200-280°and the pressure of 5-10 MPa in the reactor axial or radial type.

Along with the methanol synthesis reactions proceed at the same time the formation of byproducts, such as water, carbon dioxide, methane, esters, higher alcohols, acids, etc.

To improve the selectivity of the process, the preferential production of methanol, an important process at the optimum temperature.

Traditionally used catalytic reactors for methanol synthesis differ mainly in axial or radial movement of flow through the bed of catalyst and method of heat removal from the reaction zone.

In order to remove heat from the reaction zone, each catalyst shelf in the main gas stream is served cold the gas line. Another way of heat removal from the reaction zone is between catalyst shelves or in the catalyst layer of the reactor tube or coil heat exchangers. (Karavaev M.M., Leonov V.E., Popov I.G., Shepelev ET Technology of synthetic methanol. - M.: Chemistry, 1984, - 240 C., Il.).

The main disadvantages of the traditional method for production of synthesis gas are:

limit the pressure holding process, the conversion of natural gas in tube furnaces;

- the need to use oxygen during the process of conversion of natural gas in the mine reactors;

significant energy costs for compression of natural gas, synthesis gas and the circulating gas;

- high cost of the equipment natural gas conversion and compressors.

The disadvantages of the process of methanol synthesis are:

- the use of a less active catalyst with a relatively large size granules;

a relatively large pressure loss of gas during the passage of the granular layer of the catalyst;

- inability to secure the holding of the synthesis process at the optimum temperature;

- large size, complex structure and high cost of catalytic reactors.

The present of the invention is to provide a method of production of methanol, simplifying techno is ogechukwu scheme by carrying out the process of steam or propakistani reforming of natural gas and methanol synthesis under the same pressure of 4.0 to 12.0 MPa.

The problem is solved in that the synthesis gas by steam or propakistani catalytic conversion of hydrocarbons, such as natural gas, is carried out in a catalytic reactor radial-spiral type with the same pressure at which carry out the synthesis of methanol, 4.0 to 12.0 MPa. The conversion process is carried out in the reactor radial-spiral type with a supply of heat from outside.

You can use the pressure of natural gas supplied from wells or gas main. This allows you to exclude from the scheme compressors natural gas and synthesis gas. While the methanol synthesis will be conducted with the same or a slightly reduced pressure (due to the pressure loss in the path from the reactor conversion of hydrocarbons to the methanol synthesis reactor), which is the process of conversion of hydrocarbons, that is, from 4.0 to 12.0 MPa.

The exclusion from the scheme of the production of methanol compressor equipment will reduce capital and operating costs and increase the reliability of the installation.

Application propakistani conversion will provide a more optimal composition of synthesis gas to produce methanol.

The methanol synthesis is carried out in isothermal catalytic reactor radial-spiral type.

Note the imposition of the isothermal catalytic reactor radial-spiral type in comparison with traditionally used reactors allows you to use the most active fine-grained catalyst, to provide a process of synthesis in optimal temperature conditions, high conversion, high selectivity, the minimum amount of catalyst, the minimum pressure loss of the reaction gas passing through the granular layer of the catalyst. Completely eliminates the possibility of overheating of the catalyst.

Optimal temperature conditions for the process of methanol synthesis and high selectivity of the process is provided by an extensive heat exchange surface, placed in the catalyst layer. Maintaining the desired temperature in the catalyst layer, placed between the spiral walls is ensured by the pressure of boiling water (or other fluid) in the cavities of the spiral wall. This eliminates overheating of the catalyst, as when it was restored, and in his work.

The minimum amount of catalyst and the high degree of transformation are provided by the use of highly active fine-grained catalyst granule size 1-5 mm

Radial-spiral course of the reaction gas through the granular layer of the catalyst ensures minimal loss of pressure.

Released in the process of methanol synthesis reaction heat is fully utilized for the production of steam.

The use of methanol synthesis reactor radial spiral type PR is a stable temperature in the reaction zone during all modes of operation - when recovering a catalyst, at start-up, partial or full load.

The methanol synthesis can be carried out in one or two stages with the use of the circulation compressor.

You can also conduct a process of methanol synthesis in one or two stages with subsequent transfer of the gas after the first or second stage in the pipeline and/or for use in power installations. This will allow you to exclude from the scheme of the circulation compressor.

The invention is further explained with specific examples of its implementation and the accompanying drawings, on which:

figure 1 depicts the principal technological scheme of production of methanol from natural gas desulfurization, steam catalytic conversion of natural gas and two-stage methanol synthesis;

figure 2 - principal technological scheme of production of methanol from natural gas without desulfurization source gas, steam catalytic conversion of natural gas, with the use of air cooling units with single-stage methanol synthesis;

figure 3 - principal technological scheme of production of methanol from natural gas desulfurization, propakistani catalytic conversion of natural gas and two-stage methanol synthesis.

The proposed method for the production of methanol as follows. what a figure 1 presents the process flow diagram for production of methanol with desulfurization of natural gas, steam catalytic conversion of natural gas and two-stage methanol synthesis.

Natural gas (GHG) enters the mass transfer apparatus 1, which is purification from mechanical impurities and gas condensate (GC), passes the heater 2 natural gas, where it is heated by the gas after the steam reforming of natural gas, passes the desulfurization apparatus-hydrogenation of organic sulfur compounds 3 and the absorption of hydrogen sulfide in the apparatus 4, then mixed with steam and fed to a steam conversion of natural gas into the reactor 5. In the reactor 5 in two stages of the process of catalytic steam reforming of natural gas, with heat input at the first stage is carried out due to the heat of the synthesis gas leaving the second stage, and the supply of heat to the second stage is carried out by heat input flue gas. The synthesis gas after the steam reforming of natural gas gives off heat fresh, natural gas heater 2 natural gas, is cooled in heat exchanger 6 and is fed to the separator 7, where the separated gas condensate. Next, the synthesis gas is sent in the first step of methanol synthesis loop, is heated in the opposite heat exchanger 8 and is directed into the reactor 9 synthesis of methanol. After methanol synthesis reactor 9, the gas passes back the heat exchanger 8 and is cooled in the heat exchanger 0, where is the condensation of methanol raw. Methanol raw is separated in the separator 11, and the synthesis gas is sent to the second step of methanol synthesis loop, where it undergoes a process similar to the process in the first step of methanol synthesis loop, and the synthesis gas passes successively reverse the heat exchanger 12, the methanol synthesis reactor 13, the reverse heat exchanger 12, heat exchanger 14 and enters the separator 15. Methanol raw from the separators 11 and 15 is collected in the collection methanol, 16 and pump 17 is sent to the consumer. Part of the gas after the separator methanol 15 is sent as fuel to the burner reactor 5, and the remainder for discharge into the pipeline.

Heat of flue gas (DG) after reactor 5 is used to produce steam in the boiler 18.

Isothermal mode in reactors for methanol synthesis 9 and 13 supported by the evaporation of water in the cavities of the spiral walls, placed in the catalyst bed, and the preset temperature in the synthesis reactor is supported by the corresponding pressure in the separators 19 and 20. Supply of demineralized water (CPW) in the separators 19, 20 and 21 is carried out by the pumps 22 and 23.

When using as a raw material natural gas does not contain sulfur compounds, desulphurization may be excluded from the process flowsheet. Also water cooling can be replaced by air cooling is receiving.

Figure 2 presents a variant of the process flow diagram for production of methanol without desulfurization source gas, steam catalytic conversion of natural gas, single-stage methanol synthesis and the use of the air cooling apparatus. The gas passed through the machine clean natural gas (GHG) emissions from gas condensate and solid particles 24, the heater natural gas 25, the reactor catalytic steam reforming of natural gas 26, the heater natural gas 25, air cooler 27, the separator 28 where the separated gas condensate (GC). Next, the gas is heated in the opposite heat exchanger 29 and supplied to the methanol synthesis reactor 30. After methanol synthesis reactor 30, the gas passes back the heat exchanger 29, the air cooler 31 and enters the separator 32, where the separation of crude methanol, which is sent to the collection methanol, 33 and pump 34 is sent to the consumer.

Part of the gas after the separator 32 is sent as fuel to the burner reactor 26, and the remainder for discharge into the pipeline.

Heat of flue gas (DG) after reactor 26 is used to produce steam in the boiler 35.

Isothermal mode in the methanol synthesis reactor 30 is supported by the evaporation of water in the cavities of the spiral walls, placed in the layer kata is Isadora, and maintenance of the set temperature is supported by the corresponding pressure in the separator 36. Supply of demineralized water (CPW) in the separators 36 and 37 is carried out by the pumps 38 and 39.

Figure 3 presents a variant of the process flow diagram for production of methanol from natural gas desulfurization, propakistani catalytic conversion of natural gas and two-stage methanol synthesis.

Natural gas (GHG) enters the mass transfer apparatus 40, where it is cleaned from mechanical impurities and gas condensate (GC), passes the heater 41 natural gas, where it is heated by the gas after the steam reforming of natural gas, passes the desulfurization apparatus-hydrogenation of organic sulfur compounds 42 and absorption of hydrogen sulfide in the device 43, then mixed with water vapor and carbon dioxide and is supplied to the steam conversion of natural gas into the reactor 44. In the reactor 44 in two stages of the process of catalytic steam reforming of natural gas, with heat input at the first stage is carried out due to the heat of the synthesis gas leaving the second stage, and the supply of heat to the second stage is carried out by heat input flue gas. The synthesis gas after the steam reforming of natural gas gives off heat fresh, natural gas heater 41 natural gas, cools the I in the heat exchanger 45 and into the separator 46, where the separated gas condensate. Next, the synthesis gas is sent in the first step of methanol synthesis loop, is heated in the opposite heat exchanger 47 and sent to the reactor 48 synthesis of methanol. After methanol synthesis reactor 48, the gas passes back the heat exchanger 47, and is cooled in the heat exchanger 49 where there is condensation of methanol raw. Methanol raw is separated in the separator 50, and the synthesis gas is sent to the second step of methanol synthesis loop, where it undergoes a process similar to the process in the first step of methanol synthesis loop, and the synthesis gas passes successively reverse the heat exchanger 51, the methanol synthesis reactor 52, the reverse heat exchanger 51, the heat exchanger 53 and enters the separator 54. Methanol raw from the separators 50 and 54 is collected in the collection methanol, 55 and the pump 56 is sent to the consumer. Part of the gas after the separator methanol 54 is sent as fuel to the burner reactor 44, and the remainder for discharge into the pipeline.

Heat of flue gas (DG) after reactor 44 is used to produce steam in the boiler 57.

Isothermal mode in reactors for methanol synthesis 48 and 52 supported by the evaporation of water in the cavities of the spiral walls, placed in the catalyst bed, and the preset temperature in the synthesis reactor is supported by the corresponding pressure in the separator is 58 and 59. Supply of demineralized water (CPW) in the separators 58, 59 and 60 is carried out by the pumps 61 and 62.

An example of material flow method of producing methanol from natural gas, with steam catalytic conversion of natural gas, two-stage methanol synthesis under pressure of 7.0 MPa are presented in table 1.

td align="center"> -
Table 1.
Composition, % vol.Raw materialsBefore the reactor reforming of natural gasThe synthesis gas after the type field, these natural gasThe synthesis gas to the methanol synthesis reactor of the first stageGas after methanol synthesis reactor of the first stageGas to the methanol synthesis reactor of stage IIGas after methanol synthesis reactor of stage IIThe exhaust gas-fuelThe methanol separator methanol stage IThe methanol separator methanol II levelMethane ol-rawFlue gas
CH490.2621.495.538.711.0212.915.8419.180.470.530.006-
With2H66.491.545---------
With3H62.680.64----------
N20.560.1330.10.150.190.230.280.340.0030.004-70.12
CO20.010.0025.178.138.979.856.37.194.112.260.654.05
H2O-76.1936.440.071.40.0045.790.0149.1832.2920.3116.77
CO--8.5313.415.025.9061.662.0160.120.031-About2- 8.22
H2-- 44.2369.5460.1470.8758.4571.080.660.50-Ar - 0.84
CH3HE    13.260.2411.680.1885.45764.3879.03-
             
Consumption, nm3/h145060908388.953364217.435732910.72389.6644.3521.081116.621239
Consumption, kg/h1150.14880.14880.12425.92425.91535.61535.6895.1890.3640.5145825979.8
Vapor/gas, m3/m3 3.20.570.00070.01 0.06  0.10.480.250.2
Pressure, MPa7.07.07.07.07.07.07.07.00.030.030.030.002
Temperature, °10314.642023023023023020202020680

Table 2 shows an example of basic technical and economic indicators of methanol production capacity of 10,000 tons/year using pressure wells or gas main, confirming the effectiveness of the proposed method for production of methanol.

The pressure of natural gas taken 7 MPa, the methanol synthesis is a two - step.

Table 2.
№ p/pName of raw materials, products, auxiliary materials, wasteEditor.Value
1Natural gasnm3/t

nm3/h
1160

1450
2Water for technological needsm3/t
/br> m3/h
2,48

3,1
3Annual production from methanol raw 86% R-R (in recalculation on 100% R-R)t11664

(10000)
4Water coolingm3/t

m3/h
120

150
5ElectricitykW/ton kW/h78

97,6
6Pairs on the sidet/t

t/h
1,168

1,46
7Flue gas side (gas or fuel)m3/t

m3/h
352,4

440,5
7Specific capital expenditureRUB/t7505
8The cost t methanolRUB/t1568
9The payback period of constructionyears1,5

The increase in plant capacity for the production of methanol by the new technology will lead to a further improvement of technical and economic indicators.

Table 3 presents an example of comparison of some technical-economic indicators of methanol production capacity of 10,20 and 40 thousand tons per year.

Table 3.
Name of indicatorEd. dimensionValue
Performancet/year100002000030000
Capital expendituresRUB75,0590,06105,07
The cost of 1 t of methanolRUB/t15681061773
The payback period since completionyears1,50,80,4

1. A method of producing methanol, comprising the purification of hydrocarbons from sulfur compounds, mixing it with water vapor, obtaining synthesis gas by steam reforming of hydrocarbons under pressure in the reactor radial spiral type with the subsequent synthesis of methanol, characterized in that the conversion of hydrocarbons and methanol synthesis is carried out at the same pressure 4,0-12,0 MPa.

2. The method according to claim 1, characterized in that the methanol synthesis is carried out in isothermal catalytic reactor radial-spiral type using fine-grained catalyst granule size 1-5 mm

3. The method according to any of the C claims 1 and 2, characterized in that the methanol synthesis is carried out in one step without circulation of synthesis gas with subsequent transfer of the gas after the first stage in the pipeline and/or for use in power installations.

4. The method according to any one of claims 1 and 2, characterized in that the synthesis is carried out in two stages without circulation of synthesis gas with subsequent transfer of the gas after the second stage in the pipeline and/or for use in power installations.

5. The method according to any one of claims 1 and 2, characterized in that the synthesis is carried out in one step with the circulating synthesis gas.

6. The method according to any one of claims 1 and 2, characterized in that the synthesis is carried out in two stages with the circulating synthesis gas.

7. A method of producing methanol, comprising mixing the hydrocarbon with water vapor and carbon dioxide, synthesis gas by propakistani conversion of hydrocarbons under pressure in the reactor radial spiral type with the subsequent synthesis of methanol, characterized in that the conversion of hydrocarbons and methanol synthesis is carried out at the same pressure 4,0-12,0 MPa.

8. The method according to claim 7, characterized in that the methanol synthesis is carried out in isothermal catalytic reactor radial-spiral type using fine-grained catalyst granule size 1-5 mm

9. The method according to any of PP-8, characterized in that the methanol synthesis is carried out in one step without circulation of synthesis gas with subsequent transfer of the gas after the first stage in the pipeline and/or for use in power installations.

10. The method according to any of claims 7 to 8, characterized in that the synthesis is carried out in two stages without circulation of synthesis gas with subsequent transfer of the gas after the second stage in the pipeline and/or for use in power installations.

11. The method according to any of claims 7 and 8, characterized in that the synthesis is carried out in one step with the circulating synthesis gas.

12. The method according to any of claims 7 and 8, characterized in that the synthesis is carried out in two stages with the circulating synthesis gas.



 

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FIELD: petrochemical industry.

SUBSTANCE: the invention is dealt with petrochemical industry, in particular with a method of catalytic preliminary reforming of the hydrocarbon raw materials containing higher hydrocarbons. The method provides for the indicated hydrocarbon raw materials gating through a zone of a catalyst representing a fixed layer containing a noble metal on magnesia oxide (MgO) and-or spinel oxide (MgAl2O4) at presence of oxygen and water steam. The technical result is a decrease of a carbon share on the catalyst.

EFFECT: the invention allows to decrease a carbon share on the catalyst.

3 cl, 2 tbl, 2 ex

FIELD: electric power and chemical industries; methods of production of the electric power and liquid synthetic fuel.

SUBSTANCE: the invention presents a combined method of production of the electric power and liquid synthetic fuel with use of the gas turbine and steam-gaseous installations and is dealt with the field of electric power and chemical industries. The method provides for the partial oxidation of hydrocarbon fuel in a stream of the compressed air taken from the high-pressure compressor of the gas turbine installation with its consequent additional compression, production of a synthesis gas, its cooling and ecological purification, feeding of the produced synthesis gas in a single-pass reactor of a synthesis of a liquid synthetic fuel with the partial transformation of the synthesis gas into a liquid fuel. The power gas left in the reactor of synthesis of liquid synthetic fuel is removed into the combustion chamber of the gas-turbine installation. At that the degree of conversion of the synthesis gas is chosen from the condition of maintenance of the working medium temperature at the inlet of the gas turbine depending on the type of the gas-turbine installation used for production of the electric power, and the consequent additional compression of the air taken from the high-pressure compressor of the gas-turbine installation is realized with the help of the gas-expansion machine powered by a power gas heated at the expense of the synthesis gas cooling before the reactor of synthesis. The invention allows simultaneously produce electric power and synthetic liquid fuels.

EFFECT: the invention ensures simultaneous production of electric power and synthetic liquid fuels.

2 cl, 2 dwg

FIELD: alternate fuel manufacture catalysts.

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13 cl, 2 tbl, 17 ex

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EFFECT: process with improved characteristics due to temperature controlling in reactor.

3 cl, 1 dwg

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